ACCEPTED MANUSCRIPT
4
.1.5.3.
6-(3-allyl-5-nitro-2-phenyl-1H-indol-1-yl)-5-amino-4,5-dihydro-1,2,4-triazine-
3
(2H)-thione (5c)
-1
Yield: 74%; m.p. 198-202 ºC; IR (KBr) υ (cm ): 3096 (C-H Ar str), 2948 (C-H str), 1630 (N-
C=N str), 1600, 1470 (C=C str), 1563 (Het. Triazine str), 1531 (C=C Ar str), 1325 (NO str);
2
1
HNMR (300 MHz, DMSO-d ) δ: 2.17 (m, 1H, CH=CH , J = 1.6 Hz), 3.11 (d, 2H, CH , J = 6.5
6
2
2
Hz), 3.97 (s, 1H, 5”CH), 4.19 (brs, 2H, 5”NH , D O exchangeable), 5.06 (d, 1H, H =CH , J =
2
2
A
2
1
.8 Hz), 5.35 (dd, 1H, H =CH , J = 0.8 Hz, J = 1.8 Hz, J = 6.6 Hz), 7.15 (dd, 1H, 6CH, J = 2.2
B 2
Hz, J = 8.2 Hz), 7.27-7.38 (m, 3H, 3’,4’,5’CH, J = 4.9 Hz, J = 8.9 Hz), 7.70 (d, 2H, 2’,6’CH, J =
.30 Hz), 7.95 (d, 1H, 7CH, J = 8.4 Hz), 8.71 (s, 1H, 4CH), 9.02 (brs, 1H, 4”NH, D O
7
2
1
3
exchangeable), 12.22 (brs, 1H, 2”NH, D O exchangeable); CNMR δ (ppm) (DMSO-d , TMS):
2
6
3
5.1 (CH ), 66.3 (5”CH), 108.5 (C-7), 109.2 (C-3), 114.7 (CH=CH ), 116.7 (C-6), 124.5
2 2
(
(
(
2’,6’CH), 127.1 (4’CH), 127.3 (C-4), 127.8 (CH-C (q) fused carbon), 128.4 (3’,5’CH), 130.6
C-2), 132.4 (C-5), 133.8 (1’CH), 134.9 (CH=CH ), 140.5 (C-N (q) fused carbon), 161.0
2
18 6 2
6”CH), 185.2 (C=S); MS (70 ev): m/z = 407.00 (M+1); Anal. Calcd. for C20H N O S (406.46):
C, 59.10; H, 4.46; N, 20.68, Found, C, 59.15; H, 4.52; N, 20.62.
4
.1.5.4.
6-(3-allyl-2-phenyl-5-(trifluoromethyl)-1H-indol-1-yl)-5-amino-4,5-dihydro-
1
,2,4-triazine-3(2H)-thione (5d)
-1
Yield: 79%; m.p. 210-215 ºC; IR (KBr) υ (cm ): 3099 (C-H Ar str), 2941 (C-H str), 1620 (N-
C=N str), 1602, 1475 (C=C str), 1546 (Het. Triazine str), 1535 (C=C Ar str), 1164 (C-F str);
1
HNMR (300 MHz, DMSO-d ) δ: 2.11 (m, 1H, CH=CH , J = 1.4 Hz), 3.08 (d, 2H, CH , J = 6.8
6
2
2
Hz), 3.95 (s, 1H, 5”CH), 4.25 (brs, 2H, 5”NH
2
, D
2
O exchangeable), 5.06 (d, 1H, H
A 2
=CH , J =
1
3
2
.7 Hz), 5.30 (dd, 1H, H =CH , J = 0.6 Hz, J = 1.7 Hz, J = 6.7 Hz), 7.22-7.35 (m, 3H,
B 2
’,4’,5’CH, J = 4.7 Hz, J = 8.6 Hz), 7.54 (dd, 1H, 6CH, J = 2.0 Hz, J = 8.0 Hz), 7.68 (d, 2H,
’,6’CH, J = 7.26 Hz), 7.87 (d, 1H, 7CH, J = 8.1 Hz), 8.86 (s, 1H, 4CH), 9.04 (brs, 1H, 4”NH,
1
3
D O exchangeable), 12.20 (brs, 1H, 2”NH, D O exchangeable); CNMR δ (ppm) (DMSO-d ,
2
2
6
TMS): 35.3 (CH ), 66.4 (5”CH), 109.4 (C-3), 111.5 (C-7), 114.8 (CH=CH ), 115.1 (C-6), 117.4
2
2
(
C-4), 124.0 (2’,6’CH), 124.4 (CF ), 125.5 (C-5), 127.7 (4’CH), 128.0 (CH-C (q) fused carbon),
3
1
1
28.4 (3’,5’CH), 130.5 (C-2), 133.1 (1’CH), 134.6 (C-N (q) fused carbon), 135.3 (CH=CH2),
61.0 (6”CH), 185.5 (C=S); MS (70 ev): m/z = 430.09 (M+1); Anal. Calcd. for C H F N S
2
1
18
3
5
(429.46): C, 58.73; H, 4.22; N, 16.31, Found, C, 58.78; H, 4.17; N, 16.35.
4
.1.5.5.
6-(3-allyl-5-methoxy-2-phenyl-1H-indol-1-yl)-5-amino-4,5-dihydro-1,2,4-
triazine-3(2H)-thione (5e)
Yield: 76%; m.p. 203-208 ºC; IR (KBr) υ (cm ): 3092 (C-H Ar str), 2955 (C-H str), 1618 (N-
-1
C=N str), 1592, 1475 (C=C str), 1560 (Het. Triazine str), 1533 (C=C Ar str), 1252 (C-O-C str);
1
6 2 2
HNMR (300 MHz, DMSO-d ) δ: 2.10 (m, 1H, CH=CH , J = 1.5 Hz), 3.12 (d, 2H, CH , J = 6.6
Hz), 3.68 (s, 3H, OCH ), 3.99 (s, 1H, 5”CH), 4.21 (brs, 2H, 5”NH , D O exchangeable), 5.07 (d,
3
2
2
1
1
H, H
A
=CH
2
B 2
, J = 1.5 Hz), 5.34 (dd, 1H, H =CH , J = 0.7 Hz, J = 1.8 Hz, J = 6.5 Hz), 7.07 (dd,
H, 6CH, J = 2.2 Hz, J = 8.3 Hz), 7.26-7.37 (m, 3H, 3’,4’,5’CH, J = 4.8 Hz, J = 8.4 Hz), 7.69 (s,
1
1